2-(Nitromethylene)-hexahydropyrimidines

ABSTRACT

Novel insecticidal 2-(nitromethylene)-1,3-diazacycloalkanes.

This application is a division of copending application Ser. No.510,100, filed Sept. 27, 1974 which was a continuation-in-part ofapplication Ser. No. 412,373, filed Nov. 1, 1973, now abandoned.

DESCRIPTION OF THE INVENTION

It has been found that useful insecticidal activity is possessed bycertain 2-(nitromethylene)-1,3-diazacycloalkanes. These compounds havebeen found to be resonance hybrids, the principle forms contributingthereto being described by the formulae; : ##SPC1##

(wherein the symbols have the respective meanings set out hereinafter),which also can exist in two tautomeric forms: one form being theresonance hybrid described above and the other being described by theformula: ##SPC2##

This form (C) can be designated as a2-(nitromethyl)-1,3-diaza-2-cycloalkene. The left-hand form (A) can bedesignated as a 2-(nitromethylene)-1,3-diazacycloalkane, while theright-hand form (B) can be designated as a2-(aci-nitromethyl)-1,3-diazacycloalkanonium hydroxide inner salt.

The resonance hybrid may exist as either of two geometric isomers,depending upon the spatial relationship of the moieties about the bondbetween the carbon atom of the nitromethylene moiety and the ring carbonatom to which it is joined.

In this specification, for the sake of simplicity, these compounds willbe referred to generally as 2-(nitromethylene)-1,3-diazacycloalkanes.This term is intended to include all of the contributors to theresonance hybrid, the geometric isomers, and the tautomers, as well asmixtures thereof.

In these compounds, the respective symbols have the following meanings:n is two, three or four; when n is two or three, R¹ is straight-chainalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, or amino; R² ishydrogen, middle halogen (i.e., Cl or Br) or phenylthio, optionallysubstituted by one or more of middle halogen, nitro or alkyl or alkoxyof from one to three carbon atoms; R³ is alkyl, and m is zero or one;when n is four, R¹ is alkyl or alkenyl, R² is hydrogen and m is zero.

The invention also includes derivatives of the tautomeric form (C)wherein the alpha-hydrogen is replaced--for example, by halogen,particularly middle halogen.

In all cases, each alkyl, alkenyl, alkynyl or alkylene moiety containsno more than eight, or preferably no more than six, carbon atoms; eachmay, unless otherwise expressly indicated, be of straight-chain orbranched-chain configuration.

Of particular interest is the sub-class of this genus of compoundswherein n = 2 or 3, R¹ is C₁₋₃ alkyl, alkenyl, haloalkenyl or alkynyl,R² is hydrogen or middle halogen (Cl or Br) and m = 0. Of these, highestactivity has been associated with the compounds wherein n = 2 or 3, R¹is methyl, ethyl, 2-propenyl, 3-chloro-2-propenyl, or 2-propynyl, and R²is hydrogen, phenylthio or 4-methoxyphenylthio.

Compounds of the invention can be prepared by five procedures:

Method A - treating a nitroketene dimethyl mercaptole (NKDM) with adiamine, including suitably substituted diamines (referring to thedefinition of R¹ and R³); R. Gompper and H. Schaefer, Berichte, 100, 591(1967); Method B - substituting a moiety on the NH function of a2-(nitromethylene)-1,3-diazacycloalkane (NMDCA); a method for preparingthe latter kind of compound is disclosed in Gompper and Schaefer, supra;

Method C - reaction of trichloronitroethylene (TCNE) (G. B. Bachmann, etal, J. Org. Chem. 25, 1312 (1960); U.S. Pat. No. 3,054,828) with adiamine including suitably substituted diamines.

Method D - direct halogenation of compounds prepared by any of the abovemethods.

Method E - Compounds of this invention wherein R² is an optionallysubstituted phenylthio moiety can be prepared by reacting the precursorwherein R² is hydrogen with the appropriate phenylsulfenyl chloride orbromide in the presence of an acid acceptor.

In Method A, the reaction is carried out by mixing the reactants in asuitable solvent at a moderately elevated temperature under anhydrousconditions. Suitably, the reaction can be carried out at from about 50°to about 100°C. Often it may be convenient to conduct the reaction atthe reflux temperature. Suitable solvents are the lower alkanols,particularly ethanol or isopropyl alcohol. In some cases it will befound desirable to employ a slight (5-10%) to moderate (50-75%) excessof the diamine reactant. The unsubstituted and appropriately substituteddiamines are generally known materials.

In Method B, the N-substitution is conveniently effected by introducingthe diazacycloalkane (NMDCA), which may be prepared by Method A, into acold anhydrous mixture of a dispersion of sodium hydride in oil anddimethylformamide as solvent in an inert atmosphere and then treatingthe resulting mixture (containing the N-sodium derivative of the NMDCA)with a halide of the moiety to be substituted; the reaction is generalfor alkylating agents. Suitably, addition of the halide is conducted ata temperature below about 10°C and is conveniently conducted at icebathtemperature. It will be found desirable in many cases to employ a slight(5-25%) excess of the sodium hydride, and a slight (5-10%) to moderate(50-75%) excess of the halide.

In Method C, the TCNE is introduced into a stirred mixture of thediamine and sodium carbonate in a suitable solvent, at a temperaturebelow about 15°C, then the reaction mixture is stirred without cooling.Suitable solvents are the lower alkanols, particularly methanol.Suitably, equivalent amounts of TCNE and sodium carbonate are employed,these being in a slight (5-10%) to moderate excess (20- 30%) relative tothe diamine. The unsubstituted and appropriately substituted diaminesare generally known materials.

In Method D, a solution of the heterocyclic compound, optionallycontaining an acid acceptor, in a suitable solvent (water is ordinarilysuitable and convenient) is treated with the halogen to replace the (orboth of the) alpha-hydrogen atom(s) on the nitromethylene (ornitromethyl)moiety. The reaction can be conducted at room temperature orsomewhat above (for example, 15°-45°C). The number of halogen atomswhich are introduced depends upon the character of R² (only if R² = Hcan two halogens be substituted readily) and in part upon the amount ofhalogen and/or acid acceptor used-- relatively, the more halogen used,the greater the substitution. In some cases, the product is sufficientlynon-basic in character that it will not form a salt with the by-producthydrogen halide, even when no acid acceptor is present. In such cases,the desired product can be recovered by extracting the reaction mixturewith a suitable non-water soluble solvent, then evaporating the solvent.Suitable solvents are the halogenated alkanes such as methylenechloride. Where the product forms the salt, the product can be recoveredby treating the reaction mixture with a base, such as sodiumbicarbonate, to spring the product, then recovering it by solventextraction of the aqueous mixture with a halogenated alkane.

In Method E, a solvent such as methylene chloride preferably is used,and the acid acceptor suitably is a tertiary alkylamine, such astriethylamine, or an aromatic amine such as pyridine. The reaction isconveniently conducted by mixing the reactants at room temperature orsomewhat below, and cooling if needed to maintain the temperature of thereaction mixture at or moderately above room temperature. Some of thephenylsulfenyl halides are known compounds. Others are readily preparedby direct halogenation of the appropriate thiol or disulfide, accordingto the procedure described by E. Kuhle, Synthesis 1970, 561-580.

The techniques for recovery and purification of the products from thefinal crude reaction mixtures are conventional and are illustrated inthe examples indicated hereinafter.

These procedures for preparing compounds of this invention areillustrated in the following examples of the preparation of particularspecies of the compounds of this invention. In all cases, the identityof the product was confirmed by elemental analyses, and by infrared andnuclear magnetic resonance spectrum analyses.

EXAMPLE 1 Method A, 1-methyl-2-(nitromethylene)imidazolidine; (1)

A mixture of 16.52 grams of NKDM, 8.14 grams of N-methylethylenediamineand 200 milliliters of absolute ethanol was refluxed for 1.5 hours. Themixture was then cooled, and the reddish brown cyrstalline products thatformed was removed by filtration. The product melting point:142.5°-143.5°C. A 6.3 gram portion of the product was recrystallizedfrom ethanol (charcoal) to give 4.8 grams of 1, as white needles,melting point: 142.5°-143.5°C.

EXAMPLE 2 Method A, Hexahydro-1-methyl-2-(nitromethylene)-pyrimidine;(2)

A mixture of 8.2 grams NKDM, 7.3 grams of N-methyl-1,3-propanediamineand 100 milliliters of absolute ethanol was reflued for 1 hour. Themixture was then cooled, precipitating 4.9 grams of 2 as tan crystals,melting point: 114° -115°C.

EXAMPLE 3 Method B, 2-(nitromethylene)-1-(2-propynyl)-imidazolidine; (3)

An ice-cooled mixture of 50 milliliters of dry dimethylformamide and1.77 grams of a 57% by weight dispersion of sodium hydride in mineraloil, maintained under nitrogen atmosphere, was treated with 5.16 gramsof 2-(nitromethylene)imidazolidine. After stirring for 1 hour, 7.97grams of propargyl bromide was added. The mixture was stirred at 10° foran additional hour, allowed to warm to room temperature, and poured into400 milliliters of saturated aqueous sodium sulfate. The product wasextracted with three 300-milliliter portions of methylene chloride. Thecombined extract was dried with magnesium sulfate and the solvent wasevaporated. Addition of ether to the residual oil gave a solid which wasrecrystallized from chloroform (charcoal) to give 3.1 grams of 3, as tancrystals, melting point: 146°-147°C.

EXAMPLE 4 Method B, 2-(nitromethylene)-1-(2-propenyl)imidazolidine; (4)

To 1.77 grams of a 57% by weight dispersion of sodium hydride in oil in50 milliliters of dry dimethylformamide was added 5.16 grams of2-(nitromethylene)imidazolidine. The mixture was cooled with an icebath,stirred and maintained under a nitrogen atmosphere. After 1.5 hours,5.08 grams of allyl bromide was added. The mixture was stirred at about10° for an additional hour, then allowed to warm to room temperature andpoured into 400 milliliters of saturated aqueous sodium sulfate. Theresulting mixture was extracted thrice with 300 milliliter portions ofmethylene chloride. The combined extract was dried (magnesium sulfate)and the solvent was evaporated. Addition of ether to the residue gave anoily red solid, which on recrystallization from chloroform (charcoal),gave 2.1 grams of 4 as tan crystals, melting point: 97°-98°.

EXAMPLE 5 Method B,Hexahydro-1-methyl-2-(nitromethylene)-1H-1,3-diazepine: (5)

By the procedure of Method A, reaction of NKDM with 1,4-diaminobutanegave hexahydro-2-(nitromethylene)-1H-1,3-diazepine, melting point:152°-154°. 3.14 grams of this compound in 25 milliliters of drydimethylformamide was treated with 0.884 gram of a 57% by weightdispersion of sodium hydride in oil and then with 2.98 grams of methyliodide. Experimental conditions and work-up were like those of Examples3 and 4. Recrystallization of the crude product from methanol gave 0.6gram of 5, as a tan solid, melting point: 88°-89°C.

EXAMPLE 6 Method C, 2-(chloronitromethylene)-1-methylimidazolidine; (6)

To a cooled (10°-15°) and stirred mixture of 3.6 grams ofN-methylethylenediamine and 8.3 grams of potassium carbonate in 50milliliters of methanol was added slowly 9.1 grams of TCNE. After 1hour, the mixture was filtered. The solid obtained by evaporation of thefiltrate was recrystallized from ethanol to give 1.5 grams of 6, meltingpoint: 145°-6° C with decomposition.

The following other species of the compounds of this invention have beenprepared, by the indicated method.

EXAMPLE 7 1-ethyl-2-(nitromethylene)imidazolidine; (7)

Method A, reacting NKDM with N-ethylethylenediamine. Melting point: 110°-111°C.

EXAMPLE 8 2-(nitromethylene)-1-propylimidazolidine (8)

Method A, reacting NKDM with N-propylethylenediamine, Melting point:147°-148°C.

Example 9 1,4-dimethyl-2-(nitromethylene)- and1,5-dimethyl-2-(nitromethylene)imidazolidine, 4/1 mixture of isomers;(9)

Method B, reacting 4-methyl-2-(nitromethylene) imidazoline with methyliodide: Melting point: 100° -102°C.

EXAMPLE 10 Hexahydro-2-(nitromethylene)-1-(2-propenyl)pyrimidine (10)

Method B, reacting hexahydro-2-(nitromethylene)pyrimidine (HNMP),prepared by Method A by reaction of NKDM with 1,3-propanediamine, withallyl bromide. Melting point: 125°-126°C.

EXAMPLE 11 Hexahydro-2-(nitromethylene)-1-(2-propynyl)pyrimidine (11)

Method B, reacting HNMP with propargyl bromide. Melting point:157°-158°C.

EXAMPLE 12 1-((E)-3-chloro-2-propenyl)-2-(nitromethylene)imidazolidine(12)

Method B, reacting 2-(nitromethylene)imidazolidine withtrans-1,3-dichloro-1-propene. Melting point: 134°-135°C.

EXAMPLE 13 (Method B) -1-(2-chloro-2-propenyl)-2-(nitromethylene)imidazolidine (13)

The sodium salt of 2-(nitromethylene)imidazolidine was prepared bytreating a mixture of 1.33 grams of a 57% by weight dispersion of sodiumhydride in oil and 35 milliliters of dimethylformamide with 3.87 gramsof 2-(nitromethylene)imidazolidine. The resulting mixture was cooled toabout 20°C and stirred while adding 3.47 grams of 2,3-dichloro-1-propenedropwise. After 2 hours, the mixture was stripped under reducedpressure. The residue was slurried in methylene chloride and filtered.The solvent was evaporated from the filtrate, and the resulting crudesolid product was recrystallized from ethanol to give 13, as tancrystals melting point: 146-147° C.

EXAMPLE 14 1-amino-2-(nitromethylene)imidazolidine (14)

Method A, NKDM being reacted with N-aminoethylene diamine. Meltingpoint: 159- 160°.

EXAMPLE 15 Method D, 2-(bromonitromethylene)-1-methylimidazolidine (15)

A stirred solution of 3.57 grams of1-methyl-2(nitromethylene)imidazolidine (Compound 1) in 25 millilitersof water was treated dropwise with 3.99 grams of bromine at roomtemperature. After 30 minutes, the reaction mixture was extracted withmethylene chloride. The extract was dried (MgSO₄) and the solvent wasevaporated to give 3.0 grams of crude product, melting point 100° (withvigorous decomposition). Recrystallization of the crude product frommethylene chloride gave 15, melting point: 97° (explodes).

EXAMPLE 16 Method D, 2-(dibromonitromethyl)-1-methyl-1,4,5,6tetrahydropyrimidine (16)

7.99 grams of bromine was added dropwise to a stirred solution of 7.85grams of Compound 2 in 50 milliliters of water. After 30 minutes themixture was treated with 4.2 grams of sodium bicarbonate in 20 millitersof water. The mixture then was extracted with methylene chloride. Theextract was dried (MgSO₄) and the solvent was evaporated to give 16,melting point: 106°-107°.

EXAMPLE 17 Method D,2-(dibromonitromethyl)-4,5-dihydro-1-methyl1H-imidazole (17)

A stirred solution of 7.15 grams of 1 and 5.3 grams of sodium carbonatein 50 milliliters of water was treated at room temperature with 16 gramsof bromine. The temperature of the mixture rose to about 45°. Afterone-half hour, the product was isolated by filtration. Recrystallizationfrom methanol/water and drying under reduced pressure at roomtemperature gave 17, melting point: 88°-90°.

EXAMPLE 18 2-(dichloronitromethyl)-4,5-dihydro-1-methyl-1H-imidazole -Method D (18)

7.08 g of chlorine was slowly bubbled into a solution of 7.15 g ofCompound 1 and 5.3 g of sodium carbonate in 70 ml of water. The mixturewarmed spontaneously. After it had cooled to room temperature, it wasextracted twice with methylene chloride. The combined extracts weredried (MgSO₄) and the solvent evaporated to give a crude product, whichwas recrystallized from ethanol to give 18 as a yellow solid, meltingpoint: 48° - 49°.

EXAMPLE 192-(dichloronitromethyl)-1,4,5,6-tetrahydro-1-methylpyrimidine - Method D(19)

By the procedure described in Example 18, Compound 2 was converted to19, as a tan solid, melting point: 92° - 93°.

EXAMPLE 20 1-((Z)-3-chloro-2-propenyl)-hexahydro-2-(Nitromethylene)pyrimidine (20 )

Method B, reacting HNMP with cis-1,3-dichloropropene. Melting point:166° (with decomposition).

EXAMPLE 21 1-((Z)-3-chloro-2-propenyl)-2-nitromethylene)imidazolidine(2)

Method B, reacting 2-(nitromethylene)imidazolidine withcis-1,3-dichloropropene. Melting point: 117° - 118°.

EXAMPLE 22 Hexahydro-2-(nitromethylene)-1-(2-propenyl)-1H-1,3-diazepine(22)

Method B, reacting hexahydro-2-(nitromethylene)-1H-1,3-diazepine withallyl bromide. Melting point: 82° - 83°.

EXAMPLE 23 1-ethyl-hexahydro-2-(nitromethylene)pyrimidine (23)

Method A, reacting NKDM with N-ethyl-1,3-propanediamine. Melting point:126° - 127°.

EXAMPLE 24 hexahydro-2 -(nitromethylene)-1-propylpyrimidine (24)

Method A, reacting NKDM with N-propyl-1,3-propanediamine. Melting point:145° - 146°.

EXAMPLE 25 Method E,1-methyl-2-(nitro(phenylthio)methylene)imidazolidine (25)

14.6 g of phenylsulfenyl chloride was added dropwise to a cooled,stirred solution of 14.3 g of Compound 1 in 250 ml of pyridine. Themixture was allowed to stand overnight at room temperature, then excesspyridine was recovered on a rotary evaporator. The residue was treatedwith 250 ml of water and the mixture extracted with methylene chloride.The combined extracts were dried and the solvent evaporated to give acrystalline solid which was triturated with ethyl acetate, then ethanol,to yield 25, as a yellow solid, melting point: 170° - 173°.

EXAMPLES 26 - 32

In the manner described in Example 25, the following further R² =phenylthio analogs were prepared from the appropriate phenylsulfenylhalides, triethylamine being used as acid acceptor, and methylenechloride as solvent.

    ______________________________________                                        Compound No.                                                                             R.sup.2 =        Melting Point                                     ______________________________________                                        26         2,4-dinitrophenylthio                                                                          189° (dec.)                                27         4-methoxyphenylthio                                                                            128 - 131°                                 28         4-methylphenylthio                                                                             145 - 150°                                 29         4-chlorophenylthio                                                                             147 - 149°                                 30         3-chlorophenylthio                                                                             134 - 137°                                 31         3-nitrophenylthio                                                                              154 - 157°                                 32         4-nitrophenylthio                                                                              165 - 170°                                 ______________________________________                                    

EXAMPLE 33 1-(2-butenyl)-2-(nitromethylene)imidazolidine (33)

Method B, 2-(nitromethylene)imidazolidine was reacted with1-chloro-2-butene. Melting point: 82° - 85°.

Compounds of this invention exhibit useful insecticidal activity, beingof particular interest for control of the larvae "caterpillar" or "worm"forms of insects of the genus Heliothis, such as H. zea (corn earworm,cotton bollworm, tomato fruitworm), H. virescens (tobacco budworm); thegenus Agrotis, such as A. ipsilon (black cutworm); the genusTrichoplusia, such as T. ni (cabbage looper), and the genus Spodoptera,such as S. littoralis (Egyptian cotton leafworm). They are also ofinterest for controlling aphids and whiteflies. Some are of interest forcontrolling houseflies. In tests that have been conducted they haveexhibited low, or no, toxicity to other insects, such as the riceweevil, 2-spotted spider mite and mosquito larva. Some act very rapidlyproviding "quick knock-down" of insects; in some cases, even though thecompound is not very toxic to the insects.

Activity of compounds of this invention with respect to insects wasdetermined by establishing the LC₅₀ dosage (in milligrams of testcompound per 100 millilters of solvent required in the solution orsuspension of test compound used as a spray) to kill 50% of the testinsects. The liquid carrier was composed of 2 parts by weight ofacetone, 8 parts by volume of water and 0.05 parts by weight of Atlox1045A, a wetting agent. The test insects were the housefly, cornearworm, cabbage looper, black cutworm, mosuito, pea aphid, rice weeviland 2-spotted spider mite. All of Compounds 1 through 9, 11, 12 and 14through 33 were inactive or slightly active to the rice weevils, mitesand mosquito larvae. With respect to the corn earworm, the LC₅₀ dosagesof all of compounds 1 through 9, 11, 12, 14 - 18, 21, 23, 25, 27, 28,and 33 were below 0.04. With respect to the pea aphid, the LC₅₀ dosagesof compounds 1 through 12, 15 - 17, 20 - 24 and 33 were below 0.01. Withrespect to the housefly, the LC₅₀ dosages of compounds 1 through 13, 16-19, 21, 23, 24 and 33 were below 0.5 Compounds 1 and 2 were also testedagainst the black cutworm and cabbage looper, the respective LC₅₀dosages being in all cases below 0.04. Compounds 1 and 2 also were foundto be very toxic to the Egyptian cotton leafworm. In tests on cotton,Compound 1 controlled larvae of the cotton bollworm and tobacco budworm.It also controlled whiteflies.

The invention includes within its scope insecticidal compositionscomprising an adjuvant -- that is, a carrier optionally a surface-activeagent -- and, as active ingredient, at least one insecticide of thisinvention. Likewise the invention includes also a method of combattinginsect pests at a locus which comprises applying to the locus aneffective amount of at least one insecticide of the invention.

The term "carrier" as used herein means a material, which may beinorganic or organic and of synthetic or natural origin, with which theactive compound is mixed or formulated to facilitate its application tothe plant, seed, soil and other object to be treatedl, or its storage,transport or handling. The carrier may be a solid or a liquid.

Suitable solid carriers may be natural and synthetic clays andsilicates, for example, natural silicas such as diatomaceous earths;magnesium silicates, for example, talcs; magnesium aluminum silicates,for example, attapulgites and vermiculities; aluminum silicates, forexample, kaolinites, montmorillonites and micas; calcium carbonate;calcium sulfate; synthetic hydrated silicon oxides and synthetic calciumor aluminium silicates; elements such as for example, carbon and sulfur;natural and synthetic resins such as, for example, coumarone resins,polyvinyl chloride and styrene polymers and copolymers; solidpolychlorophenols; bitumen, waxes such as beeswax, paraffin wax, andchlorinated mineral waxes; degradable organic solids, such as groundcorn cobs and walnut shells; and solid fertilizers, for example,superphosphates.

Many of the compounds of this invention which have been prepared haveshown substantial solubility in water, so that water will be a suitablecarrier in such cases, simplifying formulation of those activecompounds. If the water solubility of a particular compound isinsufficient, a different solvent can be used. Also, in some cases aliquid in which the toxicant is insoluble or only slightly soluble canbe used as carrier.

Examples of such solvents and liquid carriers generally are alcohols,for example, isopropyl alcohol, ketones, such as acetone, methyl ethylketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatichydrocarbons such as benzene, toluene and xylene; petroleum fractionssuch as kerosene, light mineral oils, chlorinated hydrocarbons, such ascarbon tetrachloride, perchloroethylene, trichloroethane, includingliquefied normally vaporous gaseous compounds. Mixtures of differentliquids are often suitable.

If used, the surface-active agent may be an emulsifying agent or adispersing agent or a wetting agent. It may be nonionic or ionic.Surface-active agents usually applied in formulating pesticides may beused. Examples of such surface-active agents are the sodium or calciumslats of polyacrylic acids and lignin sulfonic acids; the condensationproducts of fatty acids or aliphatic amines or amides containing atleast 12 carbon atoms in the molecule with ethylene oxide and/orpropylene oxide; fatty acid esters of glycerol, sorbitan, sucrose orpentaerythritol; fatty acid salts of low molecular weight mono-, di- andtrialkylamines, condensates of these with ethylene oxide and/orpropylene oxide; condensation products of fatty alcohols or alkylphenols for example, p-octylphenol or p-octylcresol, with ethylene oxideand/or propylene oxide; sulfates or sulfonates of these condensationproducts; alkali or alkaline earth metal salts, preferably sodium salts,of sulfuric or sulfonic acids esters containing at least 10 carbon atomsin the molecule, for example, sodium lauryl sulfate, sodium secondaryalkyl sulfates, sodium salts of sulfonated castor oil, and sodiumalkyaryl sulfonates such as sodium dodecylbenzene sulfonate; andpolymers of ethylene oxide and copolymers of ethylene oxide andpropylene oxide.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solutions, emulsifiable concentrates, emulsions,suspension concentrates or aerosols. Encapsulated formulations andcontrolled release formulations also are contemplated, as are baitformulations. Wettable powders are usually compounded to contain 25, 50or 75%w of toxicant and usually contain, in addition to solid carrier,3- 10%w of a dispersing agent and, where necessary, up to 10%w ofstabilizer(s) and/or other additives such as penetrants or stickers.Dusts are usually formulated as a dust concentrate having a similarcomposition to that of a wettable powder but without a dispersant, andare diluted in the field with further solid carrier to give acomposition usually containing 1/2-10%w of toxicant. Granules may bemanufactured by agglomeration or impregnation techniques. Generally,granules will contain 1/2-25%w toxicant and 0-10%w of additives such asstabilizers, slow release modifiers and binding agents. Emulsifiableconcentrates usually contain, in addition to the solvent, and whennecessary, co-solvent, 10-50%w/v toxicant, 2-20%w/v emulsifiers and0-20%w/v of appropriate additives such as stabilizers, penetrants andcorrosion inhibitors. Suspension concentrates are compounded so as toobtain a stable, non-sedimenting, flowable product and usually contain10- 75%w toxicant, 0-5%w of dispersing agents, 0.1-10%w of suspendingagents such as protective colloids and thixotropic agents, 0-10%w ofappropriate additives such as defoamers, corrosion inhibitors,stabilizers, penetrants and stickers, and as carrier, water or anorganic liquid in which the toxicant is substantially insoluble; certainorganic additives or inorganic salts may be dissolved in the carrier toassist in preventing sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained bydiluting a wettable powder or an emulsifiable concentrate according tothe invention with water, also lie within the scope of the presentinvention.

The compositions of the invention may also contain other ingredients,for example, other compounds possessing pesticidal, herbicidal orfungicidal properties, or attractants, such as pheromones, attractivefood ingredients, and the like, for use in baits and trap formulations.

These compositions are applied in sufficient amount to supply theeffective dosage of toxicant at the locus to be protected. This dosageis dependent upon many factors, including the carrier employed, themethod and conditions of application, whether the formulation is presentat the locus in the form of an aerosol, or as a film or as discreteparticles, the thickness of film or size of particles, the insectspecies to be controlled and the like, proper consideration andresolution of these factors to provide the necessary dosage of activematerial at the locus being within the skill of those versed in the art.In general, however, the effective dosage of toxicants of this inventionat the locus to be protected --i.e. the dosage to which the insectcontacts --is of the order of 0.001% to 0.5% based on the total weightof the formulation, though under some circumstances the effectiveconcentration will be as little as 0.0001% or as much as 2%, on the samebasis.

What is claimed is:
 1. A compound of the group consisting of compoundsof the formula: ##SPC3## derivatives thereof wherein the alpha hydrogenis replaced by middle halogen and resonance hybrids represented by theformulae: ##SPC4##wherein R¹ contains up to eight carbon atoms and isstraight-chain alkyl, haloalkyl, alkenyl, (middle halo)alkenyl oralkynyl, R² is hydrogen, middle halogen or phenylthio, optionallysubstituted by one or more of middle halogen, nitro or alkyl or alkoxyof from 1 to 3 carbon atoms, R³ is alkyl of one to eight carbon atoms,and m is 0 or 1, with the proviso that in said resonance hybrids the R³substituent may only replace a hydrogen at the carbon in the 4, 5 or 6position.
 2. A compound according to claim 1 wherein R¹ is3-chloro-2-propenyl.
 3. A compound according to claim 1 wherein R¹ is2-propynyl.